CN105819488B - Nitrogen-doped graphene loaded Cu2The preparation method of O CuO nanoneedle composites - Google Patents

Nitrogen-doped graphene loaded Cu2The preparation method of O CuO nanoneedle composites Download PDF

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CN105819488B
CN105819488B CN201610180867.9A CN201610180867A CN105819488B CN 105819488 B CN105819488 B CN 105819488B CN 201610180867 A CN201610180867 A CN 201610180867A CN 105819488 B CN105819488 B CN 105819488B
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cuo
nanoneedle
nitrogen
graphene oxide
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CN105819488A (en
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杨素玲
李刚
赵俊红
郭玮
侯琳琳
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Anyang Normal University
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    • C—CHEMISTRY; METALLURGY
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    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/02—Oxides; Hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
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    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases

Abstract

Nitrogen-doped graphene loaded Cu2The preparation method of O CuO nanoneedle composites, comprises the following steps：（1）The preparation of graphene oxide：（2）The dispersion of graphene oxide：With 50～100 mL distilled water to 50～100 mg graphene oxides, using conventional ultrasound cleaning device 1～2h of ultrasonic disperse, uniform graphene oxide water solution is obtained；（3）Graphene oxide/Schweinfurt green it is compound：In the aqueous solution of above-mentioned graphene oxide, add 1～2.0 g Schweinfurt greens, stirring 3 h of mixing to obtain uniform mixed solution；（4）Nitrogen-doped graphene loaded Cu2The preparation of O CuO nanoneedle composites.The nitrogen-doped graphene loaded Cu that this method is obtained2O CuO nanoneedle composites have potential using value in many aspects.

Description

Nitrogen-doped graphene loaded Cu2The preparation method of O-CuO nanoneedle composites
Technical field
The present invention relates to a kind of preparation method of nano composite material, more particularly to a kind of nitrogen-doped graphene load Cu2The preparation method of O-CuO nanoneedle composites, belongs to chemical field.
Background technology
Cu2O-CuO nano composite materials have special interfacial structure and electronic property, cheap cost and excellent property Can, there is important application prospect in fields such as sensor, optoelectronic device, catalysis and energy storage, therefore, Cu2O-CuO is nano combined Material is subject to researcher widely concern and research.Zhang Xiaojie in 2015 et al.（See Xiaojie Zhang, Wei Qin, Dongsheng Li et al., Metal–organic framework derived porous CuO/Cu2O composite hollow octahedrons as high performance anode materials for sodium ion batteries [J], Chemical Communications, 2015, 5: 116413-16416）Adopt with cupric Metal-organic framework be template, using high-temperature heat treatment technology, be prepared for larger micron-sized porous C uO/Cu of particle diameter2O Composite, and confirm that the composite shows preferable reversible capacity, cyclical stability, high current in lithium ion battery Charging and discharging capabilities.However, which adopts the metal-organic framework of cupric for template, high-temperature heat treatment technology（300～400 DEG C）, Production temperature is high, and preparation process is complicated, is unfavorable for industrialized production and purification；Meanwhile, prepared CuO/Cu2O granules compared with Greatly, dispersed, the peculiar specific surface area of impact material is difficult, its performance is reduced.The nitrogen-atoms that adulterate in Graphene can improve stone The performance of black alkene, which can not only improve the avtive spot that Graphene adsorbs other nano-particle, moreover it is possible to strengthen Graphene and nanometer Intergranular interaction, improves their performance, has widened significantly Graphene in terms of solaode, sensor, nanometer The application in the fields such as electronics, high-performance nanometer electronic device, composite, field emmision material, gas sensor and energy stores （See Haibo Wang, Thandavarayan Maiyalagan, and Xin Wang, Review on Recent Progress in Nitrogen-Doped Graphene: Synthesis, Characterization, and Its Potential Applications [J], Acs Catalysis, 2012, 2(5):781-794.）.Correlational study is demonstrate,proved It is bright：Nano material is anchored on N doping redox graphene, can effectively suppress the reunion of nano-particle；Receive simultaneously Rice material load can effectively improve the performance of the complex on N doping redox graphene, embody their association Same effect.For example, N doping redox graphene can effectively promote the generation of CuO nano-particle, and it is special to improve which Capacitance, charging and discharging currents density and longer service life cycle, so as to improve its electricity in ultracapacitor use Current density, power and performance（See Yiju Li, Ke Ye, Kui Cheng et al., Anchoring CuO nanoparticles on nitrogen-doped reduced graphene oxide nanosheets as electrode material for supercapacitors [J], Journal of Electroanalytical Chemistry, 2014, 727: 154–162.）.
The content of the invention
It is an object of the invention to provide a kind of nitrogen-doped graphene loaded Cu2The preparation of O-CuO nanoneedle composites Method.
Nitrogen-doped graphene loaded Cu provided by the present invention2The preparation method of O-CuO nanoneedle composites, including with Lower step：
（1）The preparation of graphene oxide：In this step, used each material adopts following amounts or adopts and following amounts phase Same ratio；2 g graphite powders are added to containing 1 ± 0.1 g K2S2O8With 1 ± 0.1 g P2O5Concentrated sulphuric acid in, at 80 DEG C Room temperature being cooled to after heating 6 h, microporous filter membrane sucking filtration then being used, and neutrality is washed to distillation, the product for obtaining is in atmosphere It is dried 24 h；Product is added in the concentrated sulphuric acid of 6 mL ice coolings, the KMnO of 1.2 g is gradually added under agitation4, 35 DEG C are stirred After mixing 2 h, 20mL distilled water is added, it is 30% H to continue thereafter with 40 mL water of addition and 2 mL mass concentrations2O2, solution is changed into Yellowish-brown, reaction terminating filter reactant, and clean to remove with the hydrochloric acid solution that the mass concentration of 150 mL is 10% respectively Metal ion and neutrality is washed to, is dried, brown yellow solution is dialysed one week, centrifugation, and use distilled water cyclic washing；It is dry It is dry, grind to obtain graphene oxide solid；
（2）The dispersion of graphene oxide：With 50～100 mL distilled water to 50～100 mg graphene oxides, using routine Ultrasonic washing instrument 1～2h of ultrasonic disperse, obtains uniform graphene oxide water solution；
（3）Graphene oxide/Schweinfurt green it is compound：1～2.0 g acetic acid is added in the aqueous solution of above-mentioned graphene oxide Copper, stirring 3 h of mixing obtain uniform mixed solution；
（4）Nitrogen-doped graphene loaded Cu2The preparation of O-CuO nanoneedle composites：By the dodecane of 0.2～0.5 g Base sodium sulfonate is added to step（3）In the mixed solution for obtaining, 2 h, then the ammonia of 30～40 mL wt. 25.0% of Deca are stirred , after stirring, the brown solution for being obtained is transferred in high-temperature high-pressure reaction kettle, 150～180 DEG C of reaction 12h, gained black Deposit is washed with water, centrifugation, 60 DEG C of dryings, obtain final product nitrogen-doped graphene loaded Cu2O-CuO nanoneedle composites；
Further, step（2）The conventional ultrasound cleaning device ultrasonic disperse frequency is 40 kHz, and power is 120 W.
The present invention positive Advantageous Effects be：One there is provided a kind of new method, be prepared for a kind of N doping stone Black alkene loaded Cu2O-CuO nanoneedle new materials.Compared with pure Graphene, nitrogen-doped graphene loaded Cu2O-CuO nanoneedle is multiple Condensation material has new property；Two be the ammonia used by this method and meanwhile provide Graphene nitrogen source and realize Graphene also Former, N doping, it is to avoid using poisonous reducing agent（Such as hydrazine hydrate etc.）；Three is the dodecyl sodium sulfate table used by this method Face activating agent effectively prevents Cu as dispersant and directed agents2The reunion of O-CuO nanoneedle, realizes Cu2O-CuO nanometer needle loads On nitrogen-doped graphene.Preparation method is simple, low production cost；Four is that the yield of composite and yield are high, Ke Yida To the requirement for quantifying production；Five is that, using hydrothermal treatment consists method, preparation method is safe and simple；The nitrogen-doped graphene that this method is obtained Loaded Cu2O-CuO nanoneedle composite has potential using value in many aspects.
Description of the drawings
Fig. 1 is the nitrogen-doped graphene loaded Cu prepared by the embodiment of the present invention 32The field of O-CuO nanoneedle composites Transmitting scanning electron microscope diagram.
Fig. 2 is nitrogen-doped graphene loaded Cu prepared by the embodiment of the present invention 32The X-ray of O-CuO nanoneedle composites The score of photoelectron spectroscopy (XPS).
Fig. 3 is nitrogen-doped graphene loaded Cu prepared by the embodiment of the present invention 32In O-CuO nanoneedle composites, Cu is first The x-ray photoelectron power spectrum (XPS) of element.
Fig. 4 is nitrogen-doped graphene loaded Cu prepared by the embodiment of the present invention 32The X-ray of O-CuO nanoneedle composites Diffracting spectrum（XRD）.
Specific embodiment
With reference to specific embodiment, accompanying drawing, the invention will be further described, for a better understanding of the present invention.
Step in the present invention（1）In used in this step for mentioning each material is using following amounts or adopts and following amounts The implication of identical ratio is：Step（1）In can directly using the amount of each material mentioned, such as step（1）That what is mentioned is corresponding 2g graphite powders, 1 ± 0.1 g K2S2O8、1 ±0.1 g P2O5, the concentrated sulphuric acid of 6 mL ice coolings, the KMnO of 1.2 g4Deng, Can be to amplify the amount of 2 times of other materials accordingly using 4g graphite powders as worked as using carrying out with each amount of substance identical ratio, At this moment 2 ± 0.2 g K are adopted2S2O8、2 ±0.2 g P2O5, the concentrated sulphuric acid of 12 mL ice coolings, the KMnO of 2.4 g4Deng.
The technical scheme of the embodiment of the present invention mainly has following steps：
（1）The preparation of graphene oxide：Round-bottomed flask is positioned in oil cauldron, appropriate concentrated sulphuric acid is imported, by 1g's K2S2O8With the P of 1 g2O5It is added in concentrated sulphuric acid, stirs, then 2 g graphite powders is added in this mixed liquor, agitating heating body System so as to 6 h are heated at 80 DEG C, flask is removed into oil bath pan, be cooled to room temperature, with distilled water diluting, then filtered with micropore Film sucking filtration, and neutrality is washed to distillation, the product for obtaining is dried 24 h in atmosphere；Product is added to into 6 mL ice coolings In concentrated sulphuric acid, the KMnO of 1.2 g is gradually added under agitation4, after 35 DEG C of 2 h of stirring, add 20 mL distilled water.Continue thereafter with 40 mL water and 2 mL mass concentrations are added to be 30% H2O2, solution is changed into yellowish-brown, reaction terminating, filtration reactant, and distinguishes Mass concentration with 150 mL is that 10% hydrochloric acid solution is cleaned to remove metal ion and be washed to neutrality, is dried, by brown color Solution is dialysed one week, resulting solution centrifugation, and uses distilled water cyclic washing；It is dried, grinding obtains final product graphene oxide solid.
（2）The dispersion of graphene oxide：Weigh 50～100 mg steps（1）The graphene oxide of preparation is measured in beaker Take 50～100 mL distilled water to pour into, using conventional ultrasound cleaning device ultrasound（120 W, 40 KHz）Disperse 2 h, configuration is uniform Graphene oxide aqueous dispersions.
（3）Graphene oxide/Schweinfurt green it is compound：1～2.0 g Schweinfurt greens are weighed, the oxidation stone configured by step 2 is poured into In the aqueous solution of black alkene, stirring 3 h of mixing obtain uniform mixed solution.
（4）Nitrogen-doped graphene loaded Cu2The preparation of O-CuO nanoneedle composites：Weigh the 12 of 0.2～0.5 g Sodium alkyl sulfonate is added in step 3 gained mixed solution, stirs 2 h;Then 30～40 mL ammonia are slowly added dropwise again（wt. 25.0%) after, stirring, gained brown solution is proceeded in high-temperature high-pressure reaction kettle, 12 h are reacted in 150～180 DEG C.Close Power supply is closed, temperature of reaction kettle is down to into room temperature.Gained black deposit centrifugation, water washing collection, 60 DEG C of dryings obtain final product N doping stone Black alkene loaded Cu2O-CuO nanoneedle composites.
Embodiment 1
（1）The preparation of graphene oxide：Round-bottomed flask is placed into oil in pot, appropriate concentrated sulphuric acid is imported, by 1g's K2S2O8With the P of 1 g2O5It is added in concentrated sulphuric acid, stirs, then 2 g graphite powders is added in this mixed liquor, agitating heating body System so as to 6 h are heated at 80 DEG C, flask is removed into oil bath pan, be cooled to room temperature, with distilled water diluting, then filtered with micropore Film sucking filtration, and neutrality is washed to distillation, the product for obtaining is dried 24 h in atmosphere；Product is added to into the dense sulfur of 6 mL ice In acid, the KMnO of 1.2 g is gradually added under agitation4, after 35 DEG C of 2 h of stirring, add 20mL distilled water.Continue thereafter with addition 40 ML water and 2 mL mass concentrations are 30% H2O2, solution is changed into yellowish-brown, reaction terminating, filtration reactant, and uses 150 mL respectively 1:10 HCl cleanings metal ion and are washed to neutrality to remove, and are dried, and brown yellow solution is dialysed one week, resulting solution from The heart, and use distilled water cyclic washing；It is dried, grinding obtains final product graphene oxide solid.
（2）The dispersion of graphene oxide：The graphene oxide of 100 mg steps 1 preparation is weighed in beaker, 50 mL are measured Distilled water is poured into, using conventional ultrasound cleaning device ultrasound（120 W, 40 KHz）Disperse 2 h, configure uniform graphene oxide Aqueous dispersions.
（3）Graphene oxide/Schweinfurt green it is compound：1.5 g Schweinfurt greens are weighed, the graphite oxide configured by step 2 is poured into In the aqueous solution of alkene, stirring 3 h of mixing obtain uniform mixed solution.
（4）Nitrogen-doped graphene loaded Cu2The preparation of O-CuO nanoneedle composites：Weigh the dodecyl sulphur of 0.3 g Sour sodium is added in step 3 gained mixed solution, is stirred 2 h, is then slowly added dropwise 40 mL ammonia again（Wt. 25.0%), stir After mixing uniformly, gained brown solution is proceeded in high-temperature high-pressure reaction kettle, 12 h are reacted in 150 DEG C.Power supply is closed, by reactor Temperature is down to room temperature.Gained black deposit centrifugation, water washing collection, 60 DEG C of dryings obtain final product nitrogen-doped graphene loaded Cu2O- CuO nanoneedle composites, yield is 93.34%；In product, nitrogen content is 5.74at.%, and copper content is 5.16at.%；Cu2O- 2.0～3.3 μm of CuO nanoneedle length, wide 50～60 nm.
Embodiment 2：
（1）The preparation of graphene oxide：Round-bottomed flask is placed into oil in pot, appropriate concentrated sulphuric acid is imported, by 1 g's K2S2O8With the P of 1 g2O5It is added in concentrated sulphuric acid, stirs, then 2 g graphite powders is added in this mixed liquor, agitating heating body System so as to 6 h are heated at 80 DEG C, flask is removed into oil bath pan, be cooled to room temperature, with distilled water diluting, then filtered with micropore Film sucking filtration, and neutrality is washed to distillation, the product for obtaining is dried 24 h in atmosphere；Product is added to into the dense sulfur of 6 mL ice In acid, the KMnO of 1.2 g is gradually added under agitation4, after 35 DEG C of 2 h of stirring, add 20mL distilled water.Continue thereafter with addition 40 ML water and 2 mL mass concentrations are 30% H2O2, solution is changed into yellowish-brown, and reaction terminating filters reactant, and respectively with 150 The 1 of mL:10 HCl cleanings are dried with removing metal ion and being washed to neutrality, and brown yellow solution is dialysed one week, resulting solution Centrifugation, and use distilled water cyclic washing；It is dried, grinding obtains final product graphene oxide solid.
（2）The dispersion of graphene oxide：The graphene oxide of 100 mg steps 1 preparation is weighed in beaker, 100 are measured ML distilled water is poured into, using conventional ultrasound cleaning device ultrasound（120 W, 40 KHz）Disperse 2 h, configure uniform graphite oxide Alkene aqueous dispersions.
（3）Graphene oxide/Schweinfurt green it is compound：2.0 g Schweinfurt greens are weighed, the graphite oxide configured by step 2 is poured into In the aqueous solution of alkene, stirring 3 h of mixing obtain uniform mixed solution.
（4）Nitrogen-doped graphene loaded Cu2The preparation of O-CuO nanoneedle composites：Weigh the dodecyl sulphur of 0.5 g Sour sodium is added in step 3 gained mixed solution, stirs 2 h;Then 40 mL ammonia are slowly added dropwise again（Wt. 25.0%), stir After mixing uniformly, gained brown solution is proceeded in high-temperature high-pressure reaction kettle, 12 h are reacted in 160 DEG C.Power supply is closed, by reactor Temperature is down to room temperature.Gained black deposit centrifugation, water washing collection, 60 DEG C of dryings obtain final product nitrogen-doped graphene loaded Cu2O- CuO nanoneedle composites, yield is 95.67%；In product, nitrogen content is 6.14at.%, and copper content is 7.24at.%；Cu2O- CuO nanoneedle is about 0.5 μm, wide about 30 nm.
Embodiment 3
（1）The preparation of graphene oxide：Round-bottomed flask is placed into oil in pot, appropriate concentrated sulphuric acid is imported, by 1g's K2S2O8With the P of 1 g2O5It is added in concentrated sulphuric acid, stirs, then 2 g graphite powders is added in this mixed liquor, agitating heating body System so as to 6 h are heated at 80 DEG C, flask is removed into oil bath pan, be cooled to room temperature, with distilled water diluting, then filtered with micropore Film sucking filtration, and neutrality is washed to distillation, the product for obtaining is dried 24 h in atmosphere；Product is added to into the dense sulfur of 6 mL ice In acid, the KMnO of 1.2g is gradually added under agitation4, after 35 DEG C of 2 h of stirring, add 20mL distilled water.Continue thereafter with addition 40 ML water and 2 mL mass concentrations are 30% H2O2, solution is changed into yellowish-brown, and reaction terminating filters reactant, and respectively with 150 The 1 of mL:10 HCl cleanings are dried with removing metal ion and being washed to neutrality, and brown yellow solution is dialysed one week, resulting solution Centrifugation, and use distilled water cyclic washing；It is dried, grinding obtains final product graphene oxide solid.
（2）The dispersion of graphene oxide：The graphene oxide of 60 mg steps 1 preparation is weighed in beaker, 50 mL are measured Distilled water is poured into, using conventional ultrasound cleaning device ultrasound（120 W, 40 KHz）Disperse 2 h, configure uniform graphene oxide Aqueous dispersions.
（3）Graphene oxide/Schweinfurt green it is compound：2.0 g Schweinfurt greens are weighed, the graphite oxide configured by step 2 is poured into In the aqueous solution of alkene, stirring 3 h of mixing obtain uniform mixed solution.
（4）Nitrogen-doped graphene loaded Cu2The preparation of O-CuO nanoneedle composites：Weigh the dodecyl sulphur of 0.5 g Sour sodium is added in step 3 gained mixed solution, stirs 2 h;Then 40 mL ammonia are slowly added dropwise again（Wt. 25.0%), After stirring, gained brown solution is proceeded in high-temperature high-pressure reaction kettle, 12 h are reacted in 180 DEG C.Power supply is closed, will reaction Kettle temperature degree is down to room temperature.Gained black deposit centrifugation, water washing collection, 60 DEG C of dryings obtain final product nitrogen-doped graphene loaded Cu2O- CuO nanoneedle composites, yield is 96.81%.
The nitrogen-doped graphene loaded Cu2Field emission scanning electron microscope photo such as Fig. 1 institutes of O-CuO nanoneedle composites Show, it will be noted from fig. 1 that uniform Cu2O-CuO nanoneedle is supported on graphene film, and the length of nanoneedle 0.4～ 0.5 μm, wide 15～20 nm；
Fig. 2 is nitrogen-doped graphene loaded Cu2The XPS of O-CuO nanoneedle composites scans total collection of illustrative plates, as it is clear from fig. 2 that Compared to graphene oxide, in prepared composite, there is N and copper, show the successful doping of N and copper, oxygen in Fig. 2（O） Peak is acutely reduced, it was demonstrated that in product, graphene oxide is successfully reduced, and by XPS quantitative analyses, in product, N content is 7.32at.%.Copper content 8.56at.%；
Fig. 3 is nitrogen-doped graphene loaded Cu2The XPS swarmings of Cu 2p3/2, Cong Zhongke in O-CuO nanoneedle composites To be clearly observed two swarmings of 934.2 eV and 932.5 e, they are belonging respectively to Cu2+And Cu+, Cu2+With Cu+Ratio is about For 4.01, it was demonstrated that Cu2O-CuO coexists；
Fig. 4 is the corresponding XRD spectrum of product.A peaks in figure at 26.0 ° belong to the characteristic feature peak of Graphene；In figure Cu2The characteristic peak of O（B peaks）Respectively at 29.7 °, 36.4 °, 42.3 °, 61.4 °, correspond respectively to（110）、（111）、（200）、 （220）Four crystal faces；The characteristic peak of CuO（C peaks）32.5 °, 35.5 °, 38.7 °, 48.8 °, 53.4 °, 58.5 °, 61.4 °, 66.5 °, 68.1 °, correspond respectively to（110）、（11-1）、（111）、（20-2）、（022）、（31-1）、（11-3）、（31-1）、 （220）Nine crystal faces.

Claims (2)

1. nitrogen-doped graphene loaded Cu2The preparation method of O-CuO nanoneedle composites, it is characterised in that：Including following step Suddenly：
（1）The preparation of graphene oxide：In this step, used each material adopts following amounts or adopts and following amounts identical Ratio；2 g graphite powders are added to containing 1 ± 0.1 g K2S2O8With 1 ± 0.1 g P2O5Concentrated sulphuric acid in, heat 6 at 80 DEG C Room temperature being cooled to after h, microporous filter membrane sucking filtration then being used, and neutrality is washed to distillation, the product for obtaining is dried 24 in atmosphere h；Product is added in the concentrated sulphuric acid of 6 mL ice coolings, the KMnO of 1.2 g is gradually added under agitation4, 35 DEG C of 2 h of stirring Afterwards, 20mL distilled water is added, it is 30% H to continue thereafter with 40 mL water of addition and 2 mL mass concentrations2O2, solution is changed into yellowish-brown Color, reaction terminating filter reactant, and clean to remove metal with the hydrochloric acid solution that the mass concentration of 150 mL is 10% respectively Ion and neutrality is washed to, is dried, grinds to obtain graphene oxide solid；
（2）The dispersion of graphene oxide：With 50～100 mL distilled water to 50～100 mg graphene oxides, using conventional Ultrasound Ripple cleaning device 1～2h of ultrasonic disperse, obtains uniform graphene oxide water solution；
（3）Graphene oxide/Schweinfurt green it is compound：1～2.0 g Schweinfurt greens are added in the aqueous solution of above-mentioned graphene oxide, Stirring 3 h of mixing obtain uniform mixed solution；
（4）Nitrogen-doped graphene loaded Cu2The preparation of O-CuO nanoneedle composites：By the dodecyl sodium sulfonate of 0.2～0.5 g Sodium is added to step（3）In the mixed solution for obtaining, 2 h, then the ammonia of 30～40 mL wt. 25.0% of Deca, stirring are stirred After uniform, the brown solution for being obtained is transferred in high-temperature high-pressure reaction kettle, 150～180 DEG C of reaction 12h, gained black sediment Thing is washed with water, centrifugation, 60 DEG C of dryings, obtain final product nitrogen-doped graphene loaded Cu2O-CuO nanoneedle composites.
2. nitrogen-doped graphene loaded Cu according to claim 12The preparation method of O-CuO nanoneedle composites, which is special Levy and be：Step（2）The conventional ultrasound cleaning device ultrasonic disperse frequency is 40 kHz, and power is 120 W.
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